Catalyst and method of preparing unsaturated acids and aldehydes



United States Patent 'Int. Cl. Blllj 11/82 US. Cl. 252-437 6 Claims ABSTRACT OF THE DISCLOSURE Catalysts containing molybdenum oxide, telluriurn oxide and bismuth or antimony phosphates are useful in the vapor phase oxidation of propylene or isobutylene to form acrolein and acrylic acid or methacrolein and methacrylic acid.

This is a division of application Ser. No. 483,868, filed Aug. 30, 1965, now US. Pat. 3,467,700.

This invention relates to new and useful catalysts and to a method of preparing unsaturated aldehydes and unsaturated carboxylic acids by oxidation of unsaturated hydrocarbons at an elevated temperature, and relates more particularly to catalysts comprising a mixture of a molybdenum oxide, tellurium oxide and a bismuth or antimony phosphate in a molar ratio of 100M00 10- 100To0 and 10100 of a bismuth or antimony phosphate and to a method of preparing acrolein and acrylic acid or methacrolein and methacrylic acid by passing vapors of propylene or isobutylene and an oxygen-containing gas over the catalyst at a temperature of from about 325.C. to about 550 C. The catalyst can also be designated as Mo Te M P 2 O wherein M is Bi or Sb and with the P being in the form of a phosphate i.e., each P is attached to 3 or 4 oxygen atoms.

Numerous attempts have been made in the past to prepare products of higher oxidation state from hydrocarbons, especially from the normally gaseous hydrocarbons. However, all prior catalysts and procedures for oxidizing monoolefinic gaseous hydrocarbons to monoolefinically unsaturated aldehydes or monoolefinically unsaturated carboxylic acids with the same number of carbon atoms as the hydrocarbon having serious shortcomings. The catalysts either have a very short active life, or they convert only a portion of the hydrocarbon to desired end groups per pass; they oxidize the hydrocarbon excessively to form high proportions of carbon monoxide or carbon dioxide or both; they are not sufficiently selective, so that the hydrocarbon molecule is attacked at both the olefinic unsaturation and at a methyl group; or the oxidation of i the olefin does not proceed beyond the aldehyde stage.

It is therefore unexpected to find a catalyst having unusually long life that will convert a substantial amount, more than per pass. of a gaseous monoolefin such as propylene or isobutylene to yield very high proportions of acrolein and acrylic acid or methacrolein and methacrylic acid. It is also unexpected to find a catalyst that produces a wide range of ratios of olefinic aldehyde to monoolefinically unsaturated carboxylic'acid by controllable changes in reaction conditions or catalyst composition. Mol percent efliciencies of about 16 to 50 for the aldehyde and about 32 to 40 for the unsaturated carboxylic acid have been obtained with the catalyst and process of this invention.

3,524,823 Patented Aug. 18, 1970 ice THE REACTANTS The essential reactants are (1) propylene or isobutylene and (2) an oxygen-containing gas, which can be pure oxygen, oxygen diluted with an inert gas, oxygen enriched air or air without additional oxygen. For reasons of economy, air is the preferred oxygen-containing reactant.

For the purpose of this invention the hydrocarbons which are oxidized can be defined generically by the formula H (CH2)01 C Ila-0:011;

wherein it is also apparent that the end products formed result from the oxidation of only one methyl group on the hydrocarbon molecule while the terminal CH2=C- remains intact.

Stoichiometric ratios of oxygen to olefin for the purpose of this invention are 1.5 to 1. Slightly lower amounts of oxygen can be used at a sacrifice of yield. It is preferred, however, to use 33 to 66% excess oxygen. Larger excesses do not impair the yields of aldehydes and acids, but for practical considerations an excess much above would require extremely large equipment for a given production capacity.

The addition of steam into the reactor along with the hydrocarbon and oxygen-containing gas is desirable but not absolutely essential. The function of steam is not clear, but it seems to reduce the amount of carbon monoxide and dioxide in the efiluent gases.

Other diluent gases can be used. Surprisingly, saturated hydrocarbons such as propane are rather inert under the reaction conditions. Nitrogen or other known inert gases can be used as diluents if desired.

THE CATALYST AND ITS PREPARATION There are several methods for the preparation of the catalyst, which can be supported or unsupported. It is possible to dissolve each of the starting ingredients in water and combine them from the aqueous solutions or the ingriedients can be dry blended. Because of the more uniform blend obtained by the solution procedure, it is preferred.

A general procedure for preparing a catalyst from water-soluble ingredients is to dissolve the requisite amount of a molybdenum salt, a tellurium salt and a bismuth or antimony salt in water. Add the requisite amount of phosphoric acid to the bismuth or antimony salt solution. Add the tellurium salt solution to the molybdenum salt solution and then add the bismuth or antimony salt phosphoric acid mixture to the molybdenum-tellurium salt mixture. The catalyst is then dried and baked at 400 C. for about 16 hours.

Supported catalysts can be prepared by adding a dry support or an aqueous slurry thereof to the aqueous solution of catalyst or the aqueous catalyst ingredients can be added to the slurry of the support.

Alternatively, a slurry of the catalyst ingredients can be prepared in Water, then dried and baked. For supported catalysts the aqueous slurry of the catalyst ingredients can be added to an aqueous suspension of the support or vice versa, and then dried and baked.

Another method is to blend the dry ingredients of the desired particle size and then mix them thoroughly. Thorough blending and uniform particle size is desired.

A specific example of the solution method is now set forth.

In this procedure the ingredients are precipitated on blending.

(a) Dissolve 105.96 g. of ammonium molybdate in 300 ml. of distilled water.

(b) Dissolve 31.922 g. TeO in 80 ml. of concentrated HCl.

Add the tellurium salt solution to the ammonium molybdate solution. A precipitate forms.

(c) Dissolve 133.4 g. BiCl in water and add 46.2 g. of 85% H PO Add this mixture slowly to the precip itated ammonium molybdate-Te mixture I Dry on a steam bath and bake for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size and sieved. For supported catalysts an aqueous slurry of the support can be added to the catalyst ingredients, or vice versa, prior to drying and baking.

A supported catalyst may be prepared by adding to (c) 240 grams of an aqueous colloidal dispersion of microspheroidal silica in a concentration of 30-35% Si0 (Ludox H.S.). The silica may also be added to one of the individual ingredients or (c) added to the silica dispersion.

Among the suitable supports are silica, silica containing materials, such as diatomaceous earth, kieselguhr, silicon carbide, clay, aluminum oxides and even carbon, al-

M0O TeO2 Sb P207) 3 or bismuth or other ph0sphate The phosphate can be a P0; radical, a Pyrophosphate, or a polyphosphate.

REACTION CONDITIONS The reaction can be carried out in either a fixed or fluidized catalyst bed.

The reaction temperature can range from about 300 to 475 C. for the oxidation of propylene but the preferred range is from about 325 to about 450 C. Below 325 C. the conversion per pass is lower and low temperature tends to produce more aldehyde than desired. 'Usually, a longer contact time is needed at lower temperatures to obtain the yields of desired products obtainable at higher temperatures. Above 450 C. in the propylene oxidation some of the desired end products appear to be oxidized to carbon oxides. For isobutylene, oxidation temperatures of 375- 550 are desirable with the preferred range being 300- 450 C.

The molar ratio of oxygen to propylene or isobutylene should be at least 2 to 1 for good conversion and yields. Some excess oxygen, 33 to 66 mol percent is even more desirable and is preferred. There is no critical upper limit as to the amount of oxygen, but when air is used as the oxygen-containing gas it becomes apparent that too great an excess will required large reactors, pumping compressing and other auxiliary equipment for any given amount of desired end product. It is therefore best to limit the amount of air to provide a 33 to 66% excess of oxygen. This range provides the largest proportion of acid, under given reaction conditions. Also, since care is needed to avoid an explosive mixture, the limiting of air aids in that direction.

The molar ratio of steam to propylene or isobutylene can range from 0 to about 5 to 7, but best results are obtained with molar ratios of about 3 to 5 per mol of olefin and for this reason are preferred.

The contact time can vary considerably in the range of about 2 to 70 seconds. Best results are obtained in a range of about 8 to 54 seconds and this range is preferred.

Longer contact times usually favor the production of acid at any given temperature.

The particle size of catalyst for fixed bed operations used is from 10-18 mesh. As is known, for fixed beds, the size may be of a wider range particle size. For fluid-bed systems the catalyst size should be from -325 mesh (U.S. sieve).

The reaction can be run at atmospheric pressure, in a partial vacuum or under induced pressure up to 50-100 p.s.i. Atmospheric pressure is preferred for fixed-bed systems and a pressure of 1 to p.s.i. for fluid-bed reactions. Operation at a pressure which is below the dew point at the unsaturated acid at the reaction temperature is advantageous.

The data in the examples show that wide variations in percentages of unsaturated acids and aldehydes can be obtained with a single catalyst, using fixed ratio or reactants but changing the temperature and/or contact time. Further variation is obtainable by controlling the other variables in the reaction including the catalyst compositions within the limits set forth herein.

The examples are intended to illustrate the invention but not to limit it.

' THE EXAMPLES A series of runs was made in a fixed-bed reactor of a high silica (Vycor) glass tube 12 inches long and 30 mm. outer diameter. The reactor had three inlets, one for air, one for steam and one for propylene. Three external electrically operated heating coils were wound on the reactor. One of the coils extended along the entire length of the reactor and each of the remaining coils extended only about one-half the length of the reactor.

Outlet vapors were passed through a short water cooled condenser. Uncondensed gases were passed through a gas chromatograph (Perkin-Elmer model 154D) and analyzed continuously. The liquid condensate was weighed and then analyzed for acrylic acid and acrolein in the gas chromatograph.

The reactor was filled to about 90% of its capacity with 170 ml. of a catalyst made by the solution method described above, using a ratio of 75MoO 75Te0 and 50BiPO Empirically the catalyst is and the P is present as P0 The catalyst was not supported and had a mesh size of 10-18 (U.S. sieve).

Steam at a temperature of 200-250" C. was first passed into the reactor. Then propylene and air were separately fed into the stream of water vapor. This mixture then passed through a pre-heater and entered the reactor at about ZOO-250 C. The reactor was pre-heated to about 285 C. before the gas feed was begun.

The ratio of reactants was about 2.955 mols of oxygen and 4.36 mols of steam per mol of propylene. Cold contact time was varied as shown in the table below.

The reaction temperature was varied as the reaction proceeded.

The table below summarizes the data obtained in these runs:

Acr.acroleln. AA-acryllc acid.

For another series of runs an antimony catalyst was prepared as follows:

(a) 105.96 g. of ammonium molybdate was dissolved in ml. of distilled water at about 50 C.

(b) 31.922 g. TeO was dissolved in 80 ml. of concentrated HCl.

The tellurium salt solution was added to the ammonium molybdate solution. A precipitate formed.

91.24 g. SbC1 was dissolved in water and 69.2 g. of 85% H PO added. This mixture was added slowly to the precipitated ammonium molybdate-TeO mixture.

The mixture was dried on a steam bath and baked for 16 hours at 400 C. Thereafter, the catalyst was ground to -18 mesh size and sieved.

The reactor was filled to about 90% of its capacity with 170 ml. of this catalyst having a ratio of 75MoO 25Te0 and 12.15Sb4(P2O7)3. Empirically the catalyst is M0100T33 3Sb P1o O715 and the P is present as P O The catalyst was not supported and had a mesh size of 10-18 (U.S. sieve).

Steam at a temperature of ZOO-250 C. was first passed into the reactor. Then propylene and air were separately fed into the stream of water vapor. This mixture then passed through a pre-heater and entered the reactor at about ZOO-250 C. The reactor was pre-heated to about 285 C. before the gas feed was begun.

The ratio of reactants was about 2.955 mols of oxygen and 4.36 mols of steam per mol of propylene. Cold contact time was 45 seconds.

The reaction temperature was varied as the reaction proceeded.

The table below summarizes the data obtained in these runs:

Acr.acrolein. AA-ac1'ylle acid.

I claim:

1. A catalyst composition consisting essentially of molybdenum oxide, tellurium oxide and a bismuth or antimony phosphate in a molar ratio of 100 molybdenum oxide, 10-100 tellurium oxide and 10-100 of bismuth or antimony phosphate.

2. The composition of claim 1 on a silicic support.

3. The composition of claim 1 wherein the bismuth phosphate is BiPO 4. The composition of claim 1 wherein the antimony phosphate is Sb (P2Oq) 5. The composition of claim 3 wherein the molar ratio is about 75MoO 75Te0 and BiPO 6. The composition of claim 4 wherein the molar ratio is about Mo0 25Te0 and 12.15Sb (P O-;)

References Cited UNITED STATES PATENTS 2,941,007 6/1960 Callahan et al. 260533 3,192,259 6/1965 Fetterly 252-437 XR FOREIGN PATENTS 839,808 6/ 1960 Great Britain. 878,802 10/ 1961 Great Britain. 903,034 8/ 1962 Great Britain.

PATRICK P. GARVIN, Primary Examiner US. Cl. X.R. 260533, 604 

